Phosphonium salt assisted dyeing with anionic dyes on polyamide-polyester fibers

ABSTRACT

A method of dyeing a textile fiber selected from the group consisting of the modified polyester, polyvinyl chloride, polyacrylonitrile and cellulose acetate fibers, such method comprising dyeing the fibers with an anionic dyestuff in the presence of at least one quaternary phosphonium salt of the formula WHEREIN R, R1, R2 and R3 are each selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl and aralkyl groups of one to 18 carbon atoms and X is selected from the group consisting of halogens, alkoxy sulfate and OH group.

United States Patent [191 Shimauchi et al.

[ June 25, 1974 PHOSPHONIUM SALT ASSISTED DYEING WITH ANIONIC DYES ONPOLYAMIDE-POLYESTER FIBERS [751 Inventors: Shiro Shimauchi; NorihiroMinemura; Takeshi Matsui; Kenji Ito, all of Osaka; Takeo Shima, lwakuni;Shoji Kawase, lwakuni; Masataka Oshima, lwakuni, all of Japan [73]Assignee: Teiiin Limited, Osaka, Japan [22] Filed: Apr. 18, 1972 [21 IAppl. No.: 245,257

Related U.S. Application Data [62] Division of Ser. No. 804,294, March4, 1970, Pat.

[30] Foreign Application Priority Data [51] 1 Int. Cl D06p 5/04 [58]Field of Search 8/168, 171, 164; 260/35 P [5 6] References Cited UNITEDSTATES PATENTS 2,746,836 5/l956 Rossin 8/171 2,989,360 6/1961 Mautner8/84 X 3,584,074 6/1971 Shema et al 260/45.7 P

Primary Examiner-Donald Levy Attorney, Agent, or Firm-Sherman &Shalloway 5 7] ABSTRACT A method of dyeing a textile fiber selected fromthe group consisting of the modified polyester, polyvinyl chloride,polyacrylonitrile and cellulose acetate fibers, such method comprisingdyeing the fibers with an anionic dyestuff in the presence of at leastone quater- EiiiYlE SP'J J iPfl l of thef mvl wherein R, R R and R areeach selected from the group consisting of alkyl, alkenyl, cycloalkyl,aryl and aralkyl groups of one to 18 carbon atoms and X is selected fromthe group consisting of halogens, alkoxy sulfate and OH group.

1 Claim, N0 Drawings Q 1 PHOSPHONIUM SALT ASSISTED DYEING WITH ANIONICDYES N POLYAMIDE-POLYESTER FIBERS presence of at least one quaternaryphosphonium salt of the formula wherein R, R R and R are eachselectedfrom the group consisting of alkyl, alkenyl, cycloalkyl, aryl andaralkyl groups of one 18 carbon atoms and X is selected from the groupconsisting of halogens, alkoxy sulfate and OH group.

Fibers manufactured from such synthetic polyesters as polyethyleneterephthalate do not have any affinity at all for the ionic dyestuffsand, accordingly, they were previously dyed principally by means ofdisperse dyes. However, disperse dyes are costly and moreover the dyedproducts obtained by their use were not satisfactory with respect tobrightness. Therefore, there was a strong demand in the trade for themodification of the polyester fibers so that they could be dyed by meansof ionic dyestuffs, particularly acid dyes. It is, therefore, a primaryobject of this invention to provide a method by which modifiedpolyesters can be dyed to deep shades.

Numerous methods of dyeing polyvinyl chloride fibers are known. Forinstance, there is a dy'eing method which comprises preparing aninsoluble complex with an acid dye and a cationic surfactant and usingthis complex for dyeing the fiber; however, none of the conventionalmethods have been able to provide dyed products which are fullyv deep inshade. Therefore, a second object of the invention is to provide adyeing method by which polyvinyl chloride fibers can be dyed to fullysatisfactory deep shades.

Polyacrylonitrile fibers are usually dyed with cationic dyestuffs.However, in this case also, when expansion of the scope of color andwhen the case of dyeing of mixed spun products are considered, theimpartation f dyeability of means of the acid dyes is desirable. A thirdobject of the present invention is, therefore, to provide a dyeingmethod which expands the scope of color of the dyed products ofpolyacrylonitrile fibers as well as facilitates the dyeing of mixed spunproducts, especially mixed spun products with wool.

Cellulose acetate fibers are also dyed with disperse dyes as in the casewith polyester fibers, but in this case also the shortcoming was notedthat the brightness of the dyed product was not yet fully satisfactory.A fourth object is, therefore, to provide a dyeing method which canimpart excellent dye-ability to cellulose acetate fibers and dye thesefibers to bright shades.

Other objects and advantages of this invention will become apparent fromthe following description.

Research was conducted both from the aspect of the modification of thepolyester fiber and the method of dyeing the same. As a consequence, itwas found that shaped articles of certain classes of modified polyesterscould be dyed to exceedingly deep shades when dyed by the anionicdyestuffs in the presence of at least one compound selected from thequaternary phosphonium salts.

The quaternary phosphonium salts used in accordance with the presentinvention are those of the above st ls- $t s s amp es i sl d a.

[(OiHdaP-CHQIET' W Cl CHzCHnCHgOH Polyesters, as used herein, areprincipally intended to be polyethylene terephthalate. However, theexpression polyester also refers to those polyesters which comprise atleast 60 mol percent of ethylene terephthalate units and in which a partof the acid or dihydroxy component is substituted by one or more classesof either difunctional or hydroxy acids such as isophthalic acid,compounds having metal salts of sulfonic acid, betahydroxyethoxybenzoicacid, phydroxybenzoic acid, diphenyldicarboxylic acid,naphthalenedicarboxylic acid, diphenylsulfonedicarboxylic acid, adipicacid and sebacic acid, or the aliphatic, alicyclic and aromaticdihydroxy compounds such as diethylene glycol, trimethylene glycol,hexamethylene glycol, neopentylene glycol, 1,4- cyclohexanedimethanol,2,2,4,4-tetramethylcyclobutanediol 1,3), 1,4-bishydroxyethoxybenzene,bisphenol A and compounds having the tertiary amino group [c.g.butyl-di(beta-hydroxyethyl)amine]. Further polyesters in which a minorproportion of a monofunctional compound such as benzoylbenzoic acid and-/or a polyfunctional compound of above trifunctional such aspenta-erythritol and trimesic acid are copolymerized to a certain extentwith substantial crosslinkings are applicable. In the preparation ofthese polyesters, the known catalysts and additives such as stabilizers,delustrants, etc., can be added with no trouble at all.

The term modified polyester compositions, as used herein, refers to theblended composition of a polyamide and a polyester obtained ashereinbefore described, the blended composition of a polyamide and acopolyester obtained by copolymerizing a polyalkylene glycol with apolyester, the blended composition of a polyester and a polyamide blendcontaining a polyalkylene glycol, and the blended composition of apolyester, polyamide and polyalkylene glycol. Modified polyester fiberswhich are paritcularly desirable include: (a) those obtained bymelt-spinning a blended composition of 60 99.5 wt. percent of apolyester and 40 0.5 wt. percent of a polyamide and drawing theresulting filaments; (b) those obtained by melt-spinning a blendedcomposition of 40-05 wt. percent of a polyamide with 60 99.5 wt. percentof a copolyester obtain by copolymerizing with a polyester 1 30 wt.percent, based on the overall weight of the composition, of apolyalkylene glycol and drawing the resulting filaments; (c) thoseobtained by melt-spinning a blended composition of 99.5 60 wt. percentof a polyester and 0.5 40 wt. percent of a polyamide blend containing,based on the overall weight of the composition, of l 30 wt. percent of apolyalkylene glycol, and drawing the resulting filaments; (d) thoseobtained by melt-spinning a blended composition consisting of 60 99.5wt. percent of a polyester, 0.5 40 wt. percent of a polyamide and 0.6 30wt. percent of a polyalkylene glycol and drawing the resultingfilaments; (e) those obtained by meltspinning a blended composition of60 99.5 wt. percent of a polyester and 40 0.5 wt. percent of a polyamideand drawing the resulting filaments, then shrinking the filaments byheat treating them and thereafter redrawing the filaments; (f) thoseobtained'by meltspinning a blended composition of 60 99.5 wt. percent ofa polyester and 40 0.5 wt. percent of a polyamide, and drawing theresulting filaments, then shrinking the filaments 2 to 50 percent at atemperature ranging between 140C. and the melting temperature of thepolyester fiber and thereafter redrawing the filaments; and (g) thoseobtained by melt-spinning a blended composition of 60 99.5 wt. percentof a polyester and 40 0.5 wt. percent of a polyamide and drawing theresulting filaments, followed by shrinking the filaments by heattreating them and thereafter redrawing the filaments at a temperatureranging between room temperature and 230C. and a draw ratio ranging from2 percent to the point at which breakage of the polyester fiber takesplace.

The manufacture of a fiber by melt-spinning and drawing a blendedcomposition of a polyester and some amount of polyamide is known(British Pat. Specification No. 610,140). However, the fiber which hasbeen merely melt-spun and drawn in this manner does not demonstratedesirable dyeability when the usual 4 method of dyeing it with anionicdyestuffs is employed. It is only when the fiber is dyed by the dyeingmethod of the present invention that it is possible to provide productsdyed to bright and deep shades so as to be very useful.

As a result of further research with a view to improving the dyeabilityof the fiber itself obtained from the polyester polyamide composition,it was found that when one of the methods of the present invention,i.e.,

that wherein the fiber formed by melt-spinning and drawing theaforementioned polyester composition is y then shrunk 2 50 percent at atemperature ranging between 140C. and the melting temperature of thepolyester fiber, and thereafter it is again drawn at a temperaturebetween room temperature and 230C. and a draw ratio ranging between 2percent and the point at which its breakage takes place is employed andthe so obtained fiber is used in combination with an anionic dye and atleast one quaternary phosphonium salt as defined above, dyed productswhich are of greater 2. 2-hydroxybenzophenone series, for example, thoseof the following formulae:

wherein R is H, C H (wherein n is 1-18),

(where R is alkyl or aryl); and

wherein R is H or -SO H.

(where R is alkyl or aryl).

. 3. 2,2'-dihydroxybenzophenone series, for example, those of theformula wherein R is H, C,,H2,, (where n ll8),

4. Phenylsalicylic acid series, for example, those of the formulawherein R is H, c,.ii2,,; (wherein n 1-18),

(where R is alkyl or aryl).

5. Substituted acrylonitrile series, for example, those of the formulaepolycaproamide, polyenanthamide, polyundecamide, polyhexamethyleneadipamide and polymetaxylene adipamide, or copolymers of these withother amidefomiing substances. These polyamidescan be used either aloneor in combinations of two or more thereof. Of these polyamides, thearomatic polyamides such, for example, as those which have copolymerizedtherewith the hexamethylene-diammonium terephthalate component giveespecially desirable results with respect to compatibility. Thesepolyamides are incorporated in the polyester in an amount of 0.5 40percent by weight, and preferably 5 to percent by weight. If the contentof polyamide is less than 0.5 percent by weight, the affinity of theresulting fiber for ionic dyestuffs is inadequate. On the other hand, ifthe content of the polyamide exceeds percent by weight, the proper tiesas a polyester fiber are lost. Accordingly, it is undesirable for thecontent of the polyamide to be outside the range indicated above.

lnaddition, the dyeability of the fiber can be further enhanced byincorporating in'the foregoing polyesters and/or polyamides in an amountnot exceeding 30 percent by weight, based on the overall weight of thefiber, a polyoxyalkylene glycol. As the polyoxyalkylene glycol, mentioncan be made of such, for example, as polyoxyethylene glycol,polyoxypropylene glycol, polyoxyethylene-oxypropylene glycol block orrandom copolymer methoxypolyoxyethylene glycol, phenoxypolyoxyethyleneglycol and octylphenoxypolyoxyethylene glycol. These polyoxyalkyleneglycols may be present in either the polyester or the polyamide, or

s in both components. It may be added either during the wherein R isalkyl or aryl.

While the amount of these ultraviolet absorbents used will varydepending upon the class of the material to be dyed, the class of thedyestuff and the concentration and bath ratio, etc., the use of about 110 percent (o.w.f.) based on the material to be dyed will do. It is alsopossible to achieve the result desired by imparting the ultravioletabsorbent to the fiber using a separate bath.

Again, the modified polyester composition of the present invention notonly possesses excellent affinity for anionic dyestuffs, as notedhereinbefore, but also demonstrates satisfactory affinity for dispersedyes. In addition, it can also be dyed satisfactorily by means of thebasic dyes in the presence of anionic substances. As anionic substances,included are inorganic acids such as sulfuric and acetic acids and thesalts thereof; and benzenesulfonic acid, toluene-sulfonic acid, higheralkylbenzenesulfonic acid, and sulfuric esters of higher alcohols andthe salts thereof; and phenols.

There are no particular restrictions as to the polyamides to be used inthe present invention. as long as they are serviceable with respect totheir thermal resistance, etc. Mention can be made of such, for example,as

early stages of the manufacture of the polyester or during the blendingof the components.

It does not matter whether the polyvinyl chloride fiber used in thepresent invention is a homopolymer, a copolymer or an after-chlorinatedproduct.

Good results can naturally be expected even if this method is applied tothe mixed woven products of polyvinyl chloride fiber and other classesof fibers. Moreover, in the case of a mixed spun product of polyvinylchloride fiber with wool, there is a great advantage in that the twofibers can be dyed with the same acid dye in a single bath.

As the polyacrylonitrile fibers to be used in the present invention,acrylic fibers that do not possess dye receptive sites are usable.Included are the Orlon (trademark of DuPont Company) type, Dynel(trademark of Union Carbide and Chemical Company) type, and the acrylicconjugated fiber. Again, it goes without saying that the presentinvention also has applicability to the mixed textile products of theforegoing fibers with other classes of fibers.

As the cellulose acetate fibers to be used in the present invention,included are the usual diacetate to triacetate fibers. Again, thepresent invention can also be applied to the cellulose acetate fibersobtained by the after acetylation technique. Again, the invention can,of course, be applied to the mixed textile products of the foregoingfibers with other classes of fibers. The

' method of the present invention is especially effective in the case ofa mixed product of acetate fibers with polyamide fibers, since bothfibers are dyeable with acid dyes.

The modified polyester fibers that can be dyed by means of the method ofthe present invention are the so-called readily dyeable polyester fiberswhose dyeability by means of disperse dyes has been improved, ashereinbefore described, by either an elevated temperature treatment orthe introduction (blending or copolymerizing) of a third component, Theterm readily dyeable polyester fibers, as used herein, denote thosefibers having a dye adsorption of at least 60 percent as determined bythe method of measurement of the rate of dye adsorption as definedbelow.

The rate of dye adsorption is determined in the following manner. Thespecimen is washed in a 100-fold amount of distilled water (70C.) for 30minutes with stirring, followed by air drying and thorough opening ofthe fiber. One gram of the so standardized specimen is weighed and dyedunder the following conditions:

After completion of the dyeing and cooling to room temperature, asuitable amount of the remaining dye liquor is taken and combined withan equal amount of CF. acetone (reagent), following which thisacetonewater lzl) mixture is diluted 25 times and the optical density ismeasured using a spectrophotometer. Next, the before-dyeing dye liquordiluted in a similar manner is measured for its optical density. Therate of dye adsorption is then obtained by the following equation, theaverage of three measurements rounded to whole numbers being used.

Dye adsorption (l -d/d,,) X 100 wherein d the optical density of thebefore-dyeing dye liquor and d the optical density of the after-dyeingremaining liquor.

Polyester fibers having a dye adsorption of below 60 percent cannotprovide satisfactory dyed products even though the method of the presentinvention is used.

If the present invention is applied to polyamide fibers (e.g. nylon) theresults are negative. This is believed to be due to the fact that thedye is not dissociated as a result of the anionic dye forming a complex,with the consequence that in the case of the polyamide fibers having dyereceptive sites the results are negative as a result in the decline inthe dye adsorption.

Further, the anionic dyestuffs, as referred to herein, denote all ofthose dyes having an anionic group, i.e., the acid dyes, direct dyes,metal complex dyes, reactive dyes and acid mordant dyes.

In practicing the present invention, the dyeing methods that can be usedinclude the various conventional methods such as the dip, padding andprinting techniques.

The dyeing conditions will vary depending upon the class and form of thetextile to be dyed and the class of dyeing method to be employed. Forinstance, in the case of the most widely practiced dip method, thedyeing conditions will be as indicated below.

In the case of the dyeing the modified polyester fiber, theaforementioned compounds are added to the dye bath in a concentration of1 I percent o.w.f. A dyeing temperature of below 100C. does not resultin a satisfactory dye adsorption, therefore a temperature exceeding100C. is required. Usually, the dyeing is carried out at a temperatureof 1 l30C. until the intended color deepness is obtained. Again, carrierdyeing can also be carried out effectively using known carriersconjointly. In addition, it is also possible to make conjoint use of theorganic and inorganic acids or salts in carrying out the dyeingoperation.

On the other hand, in the case of the method of dip dyeing polyvinylchloride fibers, the dyeing may be carried out at 50 C. using theaforesaid compounds in a concentration of about l-50 percent o.w.f.(percentage based on the weight of the material to be dyed), thoughvarying depending upon the dyestuff used. Again, carrier dyeing can alsobe carried out effectively using known carriers conjointly.

Further, in the case of the cellulose acetate and polyacrylonitrilefibers, the amount of the compounds used will differ depending upon theconcentration of the dyestuif used, but usually the amount ranges from Ito I00 percent. A dyeing temperature in the range of 80 C. is convenientand, if possible, the higher, the better. Again, carrier dyeing is alsoeffectively carried out by conjointly using known carriers.

As such known carriers, mention can be made of the phenolic compoundssuch as oand p-phenylphenol, the chlorobenzene type compounds such asmonochlorobenzene, o-dichlorobenzene and trichlorobenzene, benzoic acidand benzoic acid type compounds such as benzoic acid, and thenaphthlenic compounds such as methyl naphthalene. These carriers areadded, for example, to the dye bath as an aqueous solution in the caseof those which are watersoluble and as either a dispersion or emulsionin the case of those which are water-insoluble.

For carrying out level dyeing by dispersing the dyestuff thoroughly andfor preventing the formation of tar, it is preferred to use a suitablenonionic surfactant in the method of the present invention. Surfactantssuch as indicated are those which are usually widely used asdispersants. Included are, for example, the polyethylene glycol typesurfactants such as polyethylene glycol alkylamines, polyethylene glycolalkyl ethers and polyethylene glycol aliphatic acid esters, and theether or ester type surfactants which contain the polyhydric alcoholssuch as sorbitan aliphatic acid esters and aliphatic acid monoglyceridesas the hydrophilic group.

The textile which has been dyed in accordance with the method of thepresent invention is thoroughly soaped after its dyeing and thereaftersubmitted to reduction clearing, if necessary. The textile dyed by suchmethod still retains adequate fastness even after it has undergone theseafter treatments.

While the particulars of the principle underlying the present inventionare not yet determined, it is believed that the water dissolved ordispersed dyestuff forms a complex with the quaternary phosphoniumcompound, thereby becoming compatible and having affinity with respectto the hydrophobic fibers and simultaneously to function at times ascarrier at elevated temperature to become diffused into the interior ofthe fiber and result in the adsorption of the dye. Accordingly, thebalance of the affinity between the dyestuff and the phosphoniumcompound becomes an important factor that determines the dye adsorption.The effects contemplated by the present invention cannot be achieved byjust the insolubilization of the dye but can only be attained, ashereinbefore indicated, in only those cases where the specificphosphonium compounds are used.

With respect to the dyeing of polyvinyl chloride and polyacrylonitrilefibers, particularly preferred phosphonium salts includetributylbenzylphosphonium salts, tetrabutylphosphonium salts andtriphenylphosphonium salts. With respect to the dyeing of cellulose 9-acetate fibers, tributylallylphosphonium salts andtriphenylbutylphosphonium salts are preferred. Still further inconnection with the dyeing of modified polyester fibers, it is preferredin accordance with the present invention to employ such phosphoniumsalts as tributylbenzylphosphonium salts, tetrabutylphosphonium salts,triphenylbenzylphosphonium salts, triphenylbutylphosphonium salts andtributylarylphosphonium salts.

Also, better dye adsorption is obtained when the pH of the dye bath ison the acid side.

Next, examples will be given for further illustration of the presentinvention in detail. in the examples asp/c indicates the specificviscosity measured at 35C. using orthochlorophenol as the solvent andintrinsic viscosity is defined as sp/c in which c is concentration ingrams of polymer per 100 cc of solution. Also all parts are on a weightbasis. Dyeability was indicated by the rate of dye absorption in thecase of disperse dyes, and in the case of ionic dyes it was indicated bya qualitative indication, rate of dye adsorption and classification intogrades ranging from 1 to 10. Grade 1 denotes that no dyeing at all tookplace, while Grades 2 and higher denote that as the grade becomeshigher, the dyeing becomes better. Dyeings which are of practical useare those having ratings of Grade or higher.

Example 1 Twenty parts of polymethoxylylene adipamide (mp/c 0.59) wereblended with 180 parts of 3 mol percent isophthaliccomponentcopolymerized polyethylene terephthalate (nsp/c 1.05), afterwhich the resulting blend was melt-spun at a spinning temperatureof280C. in customary manner. The freshly spun filaments were then drawn4.42 X by means of an 85C. pin, followed by shrinking. 22 percent at205C. and thereafteragain being drawn percent at 160C.

The fibers obtained were dyed using a dye bath composed of 4 percent(o.w.f.) of an acid dye Nylomin Blue GS-4, 5 percent (o.w.f.) of aceticacid, 4 percent (o.w.f.) of nonylphenoxypolyoxyethylene glycol and 10percent (o.w.f.) of tetrabutylphosphonium bromide, and under theconditions of a bath ratio of 1:100 and 120C. X 60 minutes. A dyedproduct of deep blue shade (Grade 8-9) was'obtained.

Example 2 Twenty parts of a copolyamide ("asp/c 0.54) consisting of 70mol percent of caprolactam and 30 mol percent of hexamethylenediammoniumterephthalate were melt-blended with 80 parts of polyethyleneterephthalate (nsp/c= 1.05) at 285C. for 10 minutes, after which theresulting blend was spun at a spinning speed of 285C. in customarymanner. The freshly spun filaments were drawn 4.3 X by means of an 85C.pin, then shrunk 25 percent at a temperature of 230C. and thereafteragain drawn 10 percent at a temperature of 150C. A dye bath composed of4 percent (o.w.f.) of Nylomin Blue OS, 5 percent (o.w.f.) of aceticacid, 4 percent (o.w.f.) of nonylphenoxypolyoxyethylene glycol and 4percent (o.w.f.) of triphenylbutylphosphonium chloride was used and thefibers obtained were dyed under the conditions of a bath ratio of 1:100and 120C. X 60 minutes, with the consequence that Example 3 Thirteenparts of polyhexamethylene adipamide (nsp/c=0.63) and 87 parts ofpolyethylene terephthalate (nsp/c 1.05) were melt-blended as in Example2, and the resulting blend was melt-spun at a spinning temperature of285C. in customary manner. The freshly spun filaments were drawn 4.25 Xby means of an 87C. pin, then shrunk 30 percent at 215C. and thereafteragain drawn 15 percent at a temperature of 160C.

When the fibers obtained were dyed with the acid dye Nylomin Blue GS asin Example 2, they were dyed to a deep blue shade (Grade 8). On theother hand, they were dyed to a deep green shade (Grade 7 8) by means ofthe basic dye Malachite Green.

Example 4 Twenty parts of polymethaxylene adipamide ('nsp/c 0.59). weremelt-blended with 180 parts of 3 mol percent isophthalatecomponentcopolymerized polyethylene terephthalate (nsp/c 1.05), as inExample 2, after which the resulting blend was melt-spun at a spinningtemperature of 280C. in customary manner. The freshly spun filamentswere drawn 4.42 X by means of an 85C. pin, then shrunk 22 percent at205C., and thereafter again drawn 10 percent at 160C.

When the fibers obtained were dyed as in Example 2 with the acid dyeNylomin Blue GS, they were dyed to a deep blue shade (Grade 8 9). On theother hand, when they were dyed with the basic dye Malachite Green, theywere dyed to a deep green shade.

Example 5 In preparing a copolyamide consisting of mol percent ofcaprolactam and 30 mol percent of hexamethylenediammonium terephthalate,polyoxyethylene glycol (molecular weight about 4,000) was blendedtherewith in such an amount that the content of the latter in thecopolyamide would be 20 percent by weight. Forty parts of the blend and160 parts of polyethylene terephthalate ("asp/c 1.05) were then blendedas in Example 2 (nsp/c of the blend 0.45). This blend was spun incustomary manner at a spinning temperature of 285C. The freshly spunfilaments were then drawn 4.14 X by'means of an C. pin, then shrunk 20percent at 200C. and thereafter again drawn 17 percent at C. When thisfiber was dyed as in Example 2, it was dyed to a deep blue shade (Grade9) by means of the acid dye Nylomin Blue GS and was dyed to a deep greenshade (Grade 9) by means of the basic dye Mala chite Green.

Example 6 Example 2. They were dyed to a deep blue shade (Grade 8) bymeans of acid dye Nylomin Blue GS and to a deep green shade (Grade 7) bymeans of the basic dye Malachite Green.

Example 7 The polyvinyl chloride fiber Valren (trademark of TeijinLimited) was dipped in a dye bath of the following composition where itwas dyed at 100C. for 60 minutes to obtain a dyed product of a deep blueshade.

Suminol Fast Blue PR (C. 1. Acid Blue I29) Tributylbenzylphosphoniumbromide 10 (o w.f.) Univadine W 3 70 (o w.f.) Acetic acid 3 (o w.f.)Bath ratio 1:50

Example 8 The polyvinyl chloride fiber Tevilon was dipped in a dye bathof the following composition:

Suminol Fast Red B conc. Triphenylbutylphosphonium bromide Methylnaphthalene (carrier) Univadine W Sulfuric acid Bath ratio When thedyeing was carried out at 50C. for 90 minutes, a product dyed to a deepshade of red was obtained.

Example 9 The polyvinyl chloride fiber Valren was dipped in a dye bathof the following composition:

Kayanol Millin Yellow 3 GW Tributylbenzylphosphonium bromide Methylnaphthalene (carrier) Acetic acid Bath ratio 1:

ases When the dyeing was carried out at 100C. for 60 minutes, a productdyed to a deep shade of yellow was obtained.

Example 10 The polyacrylonitrile fiber Kanekalon was dipped in a dyebath of the same composition as that of Example 7. When the dyeing wascarried out at 100C. for 60 minutes, a product dyed to a deep shade ofblue was 7 obtained.

Example 1 l Example 12 Using as a cellulose acetate textile a crepe dechine fabric composed of diacetate fiber, this fabric. was dipped in adye bath of the following composition:

Kayacyl Sky Blue R 4 (o.w.f.) Tributylbenzylphosphonium bromide 10(o.w.f.) Univadine W 4 (o,w.f.) Sulfuric acid 3 (o.w.f.) Bath ratio 1:50

The dyeing was carried out at C. for 90 minutes and a product dyed to adeep shade of blue was obtained.

Example 13 The polyester fiber Tetoron" T-89 was dipped in a dye bath ofidentical composition as that of Example 12, wherein it was dyed at120C. for 90 minutes to yield a product dyed to a deep shade of blue.

Example 14 As a modified polyester fiber, Tetoron T-89 (dye adsorptionof 85 percent) was used, and this fiber was dipped in a dye bath of thefollowing composition:

Polar Yellow 5 GN 4 (o.w.f.) (C. 1. Acid YellowTriphenylethylphosphonium bromide 10 (o.w.f.) Univadine W 4 (o.w.f.)Orthophenylphenol 4 (o.w.f.) Acetic acid 2 (o.w.f.)

When the fiber was dyed at C. for 90 minutes, a product dyed to a deepshade (Grade 6) of yellow was obtained.

What is claimed is:

1. A method of dyeing a modified polyester textile fiber having a dyeadsorption of at least 60 percent and which is selected from the groupconsisting of:

a. that obtained by melt-spinning a blended composition of 60 99.5percent by weight of polyester and 40 0.5 percent by weight of polyamideand drawing the resulting filaments;

b. that obtained by melt-spinning a blended composition of 40 0.5percent by weight of polyamide with 60 99.5 percent by weight of acopolyester obtained by copolymerizing with a polyester 1 30 percent byweight, based on the overall weight of the composition, of apolyoxyalkylene glycol, and drawing the resulting filaments;

. that obtained by melt-spinning a blended composition of 99.5 60percent by weight of polyester and 0.5 40 percent by weight of apolyamide blend containing, based on the overall weight of thecomposition, 1 30 percent by weight of a polyoxyalkylene glycol, anddrawing the resulting filaments;

d. that obtained by melt-spinning a blended composition of 60 99.5percent by weight of polyester, 0.5 40 percent by weight of polyamideand 0.6 30 percent by weight of polyoxyalkylene glycol and drawing theresulting filaments;

-. that obtained by meltspinning a blended composition of 60 99.5percent by weight of polyester and 40 0.5 percent by weight ofpolyamide, drawing the resulting filaments, followed by heat treatingand shrinking the filaments, and thereafter again drawing the filaments;

f. that obtained by melt-spinning a blended composition of 60 99.5percent by weight of polyester and 40 0.5 percent by weight ofpolyamide, drawing the resulting filaments, followed by shrinking thefilaments 2 percent to 50 percent of their initial length by heating thefilaments at a temperature of between 140C. and the melting point ofsaid polyester filaments, and thereafter redrawing the filaments; and

. that obtained by melt-spinning a blended composiof at least onequaternary phosphonium salt of the formula wherein R, R R and R are eachselected from the group consisting of alkyl, alkenyl, cycloalkyl, aryland aralkyl groups of one to 18 carbon atoms and X is selected from thegroup consisting of halogens, alkoxy sulfate and OH group.

h UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTIUN Pate t 34819326I Dated June 25; 1974 Inventor(s) I Shiro SHIMAUCHI ET AL It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

. 'In the Headingunder "Foreign Application Priority Data",

line 7 thereof: cancel "43-61638" and substitute therefor Signed andsealed this 12th day of Nonember 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents

